Process for the preparation of liquid nitric esters



Patented July 8, 1 952 V UNITED -smss PROCESS FOR THE PREPARATION OF,

' LIQUID NITRIC ESTERS 1 Aubrey A. Young, Tamaqua, Pa., assignor to Atlas Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application April 12, 1947,

Serial No. 740,993

' 2 Claims.

The present invention relates to the preparation of nitrated ethylene glycol glucoside.

An object of the invention is the provision of an improved process for manufacturing nitrated ethylene glycol glucoside.

Another object of the invention is the provision of an improved process for washing nitrated ethylene glycol glucoside.

A further object of the invention is the provision of a process for producing dehydrated nitrated ethylene glycol glucoside.

Other objects of the invention will be apparent from the following description.

Liquid nitric esters have been used for many years in explosive compositions. Nitroglycerin is the most common of such esters, but for some time ethylene glycol has been nitrated with glycerin to produce low-freezing mixtures of nitroglycerin and nitroglycol. Various sugars such as glucose and sucrose have also been,nitrated with ethylene glycol and with glycerin to produce liquid nitric ester mixtures. Explosive liquid nitric esters generally exhibit much the same properties, and they and their mixtures are commonly called nitroglycerin even though they? contain true glycerol trinitrate only partially, or sometimes not at all.

One of the materials, the nitration of which has been suggested for use as, or in, "nitroglycerin, is ethylene glycol glucoside. It is to explosive liquid nitric esters containing this material that the present invention is directed.

Explosive liquid nitric esters are usually prepared by nitrating glycerin or other polyhydroxy materials such as described above with mixed concentrated nitric and sulphuric acids with cooling and agitation. After nitration is completed, the nitrated material and the spent mixed acids are run from the nitrating vessel to a container where the explosive liquid nitric esters, termed oil, separate from the heavier spent acids. The separated oil is then run into another container where it is emulsified with water and then permitted to separate once or several times. Following this water washing the oil is washed by emulsifying it, usually in another building, with a sodium carbonate solution. This last wash serves to remove acidity, and after it the oil is permitted to separate and is ready for use. Continuous processes which, however, utilize much the same sequence of steps are also in use, particularly abroad.

The preparation of nitrated ethylene glycol glucoside or mixtures containing it has presented difiiculties in that the emulsions formed in the obtained.

various manufacturing stepsdo not completely break and a product containing an undesirable quantity of emulsified water results.

According to the present invention explosive liquid nitric ester products containing nitrated ethylene glycol glucoside are washed with an aqueous solution of sodium carbonate and sodium chloride. This washing solution is removed from the nitrated product andthe p'roduct is mixed with finely divided sodium chloride and finally removed from thesodium chloride. By this procedure a much drier liquid nitric'ester is .The following exampleillustrates a specific embodiment of the invention.

A mixture of 640 pounds of glycerin, 640 pounds of ethylene-glycol, and 320 pounds of ethylene glycol glucoside was completely nitrated with mixed sulphuric and nitricacids in a conventional nitration procedure. 'After nitration, a mixture of. about 12/; ounces of sodium fluoride and about ounce of kieselguhr was added to the charge as a separation aid. The charge was then run through asettling tank where the oil settled out above the spent acid. I The separated oil, then at a temperature of about 40 F., was run into a washing tank containing 36 cu. ft. of water at 137 F. Air was forced into the tank through a perforated coil in the bottom of the tank to agitate and emulsify the water and oil. After the addition of the oil, the temperature of the mixture was about 106 F. This temperature is somewhat higher than that usually employed in nitroglycerin manufacturing operations since higher washing temperatures tend to produce drier products. When the mixture was completely emulsified, agitation was stopped and the oil separated out below the lighter wash water.

of a solution at F. containing 18 cu. ft. of water, pounds of soda ash, and 110 pounds of common salt was run into a tank in another building. While air was pumped in through a coil in the bottom of the tank, the oil was added to the tank, and the remainder of the solution was also added. The temperature of the resultant emulsion was 100 F., and agitation was continued until a sample of the oil, after permitting it to settle, no longer showed an acid reaction to test paper. During the neutralization about pound of wood pulp, a conventional separation aid, was added. The charge was permitted to efifects of the present invention is subject to c'on'-' siderable variation. While as little as of salt in the salt and sodium carbonate wash, based on weight of ethylene glycol glucoside, and a similar amount in the dry salt treatment is sufficient to produce dry enough oils for some pur poses, it is usually preferred to employ at, least about salt in each of the salt and sodium carbonate wash and the dry salt treatment.

The salt used in the dry salt treatment should be finely divided as it appears that the finer the salt the more effective are its water removing properties. While it usually is'preferred. to employ salt ground so that atleast passes a U. .S. S. #70 sieve, adequate results may usually be obtained when salt, so coarse that but 10% passes a U. S. S. #70 sieve, is employed.

Ethylene glycol glucoside, as commercially manufactured, is apt to contain some polyethylene glycol glucosides, and the term ethylene glycol glucoside as used herein is meant to include ethylene glycol glucoside containing proportions of polyethylene glycol glucosides.

The method of the present invention is. applicable to mixtures generally containing nitrated ethylene glycol glucoside, but usually it will be found expedient to maintain the nitrated ethylene glycol glucoside contents of explosive liquid nitric esters between about 50%, and about 5%.

What is claimed is:

l. A process for manufacturing explosiveliquid nitric esterproducts comprising nitroglycerine and between about 5% anclabout 50% of nitrated ethylene glycol glucoside, which comprises 7 washing said products with a solution of sodium '4 carbonate and sodium chloride, separating said solution from said products, adding to said products finely divided solid sodium chloride, and separating said products from said sodium chloride.

2. A process for manufacturing explosive liquid nitric ester products comprising vnitroglycerine and between about 5% and about of nitrated ethylene glycol glucoside, which comprises washing said products with a solution of sodium carbonate and sodium chloride, said salt being employed in an amount equal to at least about 10% by weight of the nitrated ethylene glycol glucoside, separating said solution from said products,=adding to said products finely divided solid sodium chloride in an amount equal to at least about 10% by weight of the nitrated ethylene glycol glucoside, and separating said products from said sodium chloride.

AUBREY A. YOUNG.

REFERENCES CITED The following references are of record in the file of this patent: 1

UNITED STATES PATENTS OTHER REFERENCES Explosives by Marshall, volume l(19l'7), published by P. Blakiston Son 81 Company, Philadelphia, Pennsylvania, page 226.

Organic Chemistry by Karrer, 2nd'edition (1946) published by Elsevier Book Company, Incorporated, New York city, page 203. 

1. A PROCESS FOR MANUFACTURING EXPOLOSIVE LIQUID NITRIC ESTER PRODUCTS COMPRISING NITROGLYCERINE AND BETWEEN ABOUT 5% AND ABOUT 50% OF NITRATED ETHYLENE GLYCOL GLUCOSIDE, WHICH COMPRISES WASHING SAID PRODUCTS WITH A SOLUTION OF SODIUM CARBONATE AND SODIUM CHLORIDE, SEPARATING SAID SOLUTION FROM SAID PRODUCTS, ADDING TO SAID PRODUCTS FINELY DIVIDED SOLID SODIUM CHLORIDE, AND SEPARATING SAID PRODUCTS FROM SAID SODIUM CHLORIDE. 